Method of stabilization with a substituted triazine and compositions stabilized thereby



METHOD OF STAEELIZATEON WITH A SUESTL This application is a divisional application of copending application Serial No. 87,520, filed February 21, 1961,

which in turn' is a' continuation-in-part of application Serial No. 47,159, filed August 3,1960, now abandoned, which in turn is a continuation-in-partnof application Serial No. 21,604, filed April 12, 1960, now abandoned.

This invention relates to a method of stabilization with a substituted triazine and to compositions stabilized thereby. The invention also relates to novel substituted tri azines.

In one aspect of the invention, the novel monohalogen substituted triazines, particularly the monochloro substituted triazines of the formula:

Rafi J7 1 wherein R represents substituted hydroxyphenyl, such as alkylhydroxyphenyl, especially having from 7 to 24 carbon atoms, e. g. methylhydroxyphenyl, ethylhydroxyphenyl, propylhydroxyphenyl, butylhydroxyphenyl, octylhydroxyphenyl, octadecylhydroxyphenyl, dimethylhydroxyphcnyl, dibutylhydroxyphenyl, etc'., or an aliphatic hydrocarbon radical, preferably alkyl having from 1 to 18 carbon atoms, 7 R represents hydroxyphenyl or substituted hydroxyphenyl, preferably alkylhydroxyphenyl having from 7 to 24 carbon atoms, e.g. methylhydroxyphenyl, ethylhydroxyphenyl, propylhydroxyphenyl, butylhydroxyphenyl, octylhydroxyphenyl, octadecylhydroxyphenyl, dimethylhydroxyphenyl, dibutylhydroxyphenyl, etc.; and 'X and Y each independently represents S, -O- or NR wherein R is aralkyl, preferably benzyl, alkyl, preferably lower alkyl, or hydrogen, are useful in stabilizing compositions of organic materials, such as e.g. polypropylene compositions,ctc.

A particularly preferred stabilizer of Formula Iis constituted by a compound of the formula:

NAN

' United States Patent M 3,22,681 Patented Aug. 24, 1955 amino, ethylhydroxyphenylamino, propylhydroxyphenylanrino, butylhydroxyphenylamino, octylhydroxyphenylamino, octadecylhydroxyphenylamino, dimethylhydroxyphenylamino, dibutylhydroxyphenylamino, etc., or aliphatic hydrocarbon radical substituted mercapto, preferably alkylmercaptohaving from 1 to 18 carbon atoms, e.g. methylmcrcapto,,ethylrnercapto, propylmerv capto, .butylmercapto, octylmercapto, dodecylmercapto, octadecylmercapto, etc.; and

R represents substituted hydroxyphenylamino, preferably alkylhydroxyphenylamino having from 7 to 24 carbon atoms, e.g. methylhydroxyphenylamino, ethylhydroxyphenylamino, propylhydroxyphenylamino, butylhydroxyphenylamino, octylhydroxyphenylamino, octadecylhydroxyphenylamino, dimethylhydroxyphenylamino, dibutyihydroxyphenylamino, etc. I In this specification, the term lower signifies a group having from 1 to 6 carbon atoms, and aryl embraces within its meaning not merely carbocyclic, e.g., phenyl, naphthyl, etc., but also heterocyclic radicals, e.g., pyridyl, thiazolyl, etc. I Up to the present time, the use of the substituted triazines of the invention in stabilizing polymeric material,

e.g., polypropylene, has not been known. It has now surprisingly been found that other organic materials are stabilized, e.g., against oxidative deterioration, by incorporating therein eflective quantities of one of the substituted stabilization is polypropylene.

Polymeric materials, such as the foregoing, find use as thermoplastic molding or coating agents. 'Moreover, because of their high dielectric strengthand their resistance to water, they are particularly useful as insulators or dielectrics in condensers and other such equipment. It is known that these polyolefins, e.g., polyethylene and polypropylene, are attacked by oxygen, particularly when exposed to the atmosphere and at elevated temperatures. For example, during use or manufacture the desirable properties of the polyolefins may be impaired due to oxi dative deterioration. Such degradation causes loss in .dielectric properties, discoloration, embrittlement, gelation, etc.

Not only homopolymeric material, but also copolymers and physical mixtures thereof are stabilized according to the present invention. For example, high impact polystyrene containing copolymers of butadiene and styrene is stabilized according to the invention.

The invention is also particularly useful in stabilizing lubricating oils of various types including aliphatic esters, such as for example dihexyl azelate, di-(Z-ethylhexyl) azelate, di- (3,5,5-trimethyl-hexyl)glutarate, di- (3,5,5-trimethylpenyl) -glutarate, di- Z-ethylhexyl pimelate, di- (2- et-hylhexyl) adipate, diisoamyl adipate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, 1,S-pentanediol-di-(Z-ethylhexanoate), etc.

The present invention also relates to the stabilizing of fatty materials including oils of animal and vegetable origin which tend to deteriorate on standing and exposure to atmospheric oxygen. Among the edible fats and oils within the scope of the present invention are: linseed oil, menhaden oil, cod liver oil, castor oil, olive oil, rapeseed oil, coconut oil, palm oil, corn oil, sesame oil, peanut oil, cotton seed oil, butter, fat, lard, beef tallow, etc. Other oils and fats which deteriorate on standing and exposure to oxygen in the air or oxygen at elevated temperatures, are all Within the scope of the invention.

Within the scope of the invention, also, are saturated and unsaturated hydrocarbons which tend to deteriorate on storage, such as for example, gasolines, both natural and synthetic, in particular, saturated and unsaturated gasolines, etc., jet fuel, diesel oil, mineral oil, fuel oil, drying oil, waxes, resins, etc. Such hydrocarbons are protected against gum formation, discoloration and other deterioration with the stabilizers of the present invention. It is, therefore, an object of the present invention to provide novel substituted triazine compounds which are versatile and effective stabilizers in at least a single class of the foregoing organic materials which are normally subject to deterioration caused by exposure to light and/ or heat and/ or oxygen, etc.

The stabilizers of the present invention are especially useful in stabilizing polyolefinic material, e.g. polypropylene and polyethylene, as well as other polymeric material, e.g. polystyrene, in particular high impact polystyrene. These triazines are also effective stabilizers for other relatively unstable organic material, eg hydrocarbon oil of mineral origin, in particular mineral oil; gasoline, both natural and synthetic; oils of animal origin, in particular, lard; oils of vegetable origin, in particular, cotton seed oil; high temperature lubricating oils, e.g. diesters of fatty acids, in particular, diesters of fatty acids having from 5 to 15 carbon atoms per molecule. Further organic materials which are effectively stabilized by these triazines comprise: aldehydes, e.g. aliphatic, such as heptaldehydes.

It is a prime object of the invention, therefore, to provide a method for stabilizing organic material, such as described hereinabove, by incorporating in said organic material a stabilizing amount of a triazine compound according to the invention.

It is understood that the stabilizers of the invention are not necessarily of equivalent potency. The specific stabilizer most useful to a given unstable material will depend upon several factors for its advantages. Availability and cost of raw materials for the manufacture of the stabilizer and effective inhibitory action of the stabilizer, including duration and degree of activity, are among the factors which control the choice of a specific stabilizer for a specific substrate which is normally subject to deterioration. Toxicity, color, stability to light and/or heat and solubility are also important factors. For example, a preferred stabilized composition according to the invention comprises from about 0.001% to about 5% by weight of a triazine stabilizer according to this invention in polypropylene.

The compounds of this invention may be used also to stabilize organic material in combination with other additive agents, such as for example, antioxidants, pourpoint depressants, corrosion and rust inhibitors, dispersing agents, demulsifiers, antifoaming agents, carbon black, accelerators and other chemicals used in rubber compounding, plasticizers, color stabilizers, heat stabilizers, UV absorbers, dyes and pigments, etc.

Compounds of the Formulae I and II are also useful as intermediates in the synthesis of valuable diand trisubstituted triazines which are themselves useful as stabilizers.

The compounds of the present invention are advantageously prepared, for example, according to the following reactions, wherein R represents the same or different NHR RSHI

RNHal NHR IIIHR In the foregoing scheme of reactions, it is understood that, while cyanuric chloride is a preferred starting material, other triazine compounds having reactive groups other than halogen may be used.

In the foregoing scheme also, the H of RSH may be replaced by a suitable reactive group or atom, as e.g. an alkali metal, such as sodium, potassium, etc., or the ammonium radical. In the case of the imino group, hydrogen may be replaced by alkyl, benzyl, etc.

For reaction with a suitable triazine, the amines and mercaptans of the formulae RNH and RSH respectively are useful. The R group is advantageously an alkyl having from 1 to 18 carbon atoms, e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. R is also advantageously a cycloalkyl group, e.g, cyclopentyl and cyclohexyl. In other aspects R is aryl, e.g., phenyl, hydroxyaryl, e.g., hydroxyphenyl, alkylaryl, e.g., alkyphenyl having from 7 to 24 carbon atoms, such as tolyl, ethylphenyl, propylphenyl, butylphenyl, octylphenyl, octadecylphenyl, etc.; alkylhydroxyaryl, e.g., alkylhydroxyphenyl, such as methylhydroxyphenyl, dimethylhydroxyphenyl, trimethylhydroxyphenyl, tetramethylhydroxyphenyl, ethylhydroxyphenyl, diethylhyroxyphenyl, triethylhydroxyphenyl, tetraethylhydroxyphenyl, propylhydroxyphenyl, dipropylhydroxyphenyl, butylhydroxyphenyl, dibutylhydroxyphenyl, octylhydroxyphenyl, dioctylhydroxyphenyl, octadecylhydroxyphenyl, etc.

Another useful class of R groups comprises the alkylthioalkyls, such as methylthiomethyl, methylthioethyl, methylthiopropyl, methylthiobutyl, methylthiopentyl, etc, also ethylthiopentyl, etc.,

propylthiomethyl, propylthioethyl, propylthiopropyl, propylthiobutyl, propylthiopentyl, etc., butylthiomethyl, butylthioethyl, butylthiopropyl, butylthiobutyl, butylthiopentyl, etc., pentylthiomethyl, pentylthioethyl, pentylthiopropyl, etc., hexylthiomethyl, hexylthioethyl, hexylthiopropyl, etc., heptylthiomethyl, heptylthioethyl, heptylthiopropyl, octylthiomethyl, octylthioethyl, etc.

Other useful R groups comprise benzyl, hydroxybenzyl and alkylhydroxybenzyl, e.g. methylhydroxybenzyl, ethylhyrodxybenzyl, propylhydroxybenzyl, butylhydroxybenzyl, octylhydroxybenzyl, etc.; cyanoalkyl, e.g. cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl, etc.; carbalkoxyalkyl, e.g. carbomethoxymethyl, carbethoxyethyl, carbopropoxyethyl, carbododecanoxyethyl, etc.; carbalkoxyphenyl, e.g. carbomethoxyphenyl, carbethoxyphenyl, carbopropoxyphenyl, carbododecanoxyphenyl, etc.

The following examples are illustrative of the invention, but by no means is the invention limited thereto. In all examples parts are by weight unless otherwise noted, and the relationship between the parts by weight and parts by volume is as that of grams to cubic centimeters. The temperature is in degrees Centigrade.

EXAMPLE 1 6- 4-hydr0xy-3 ,5 -di-t-butylanil ino) -2,4-dichlr0- 1,3,5-triazine (a) 4-nitroso-2,6-di-t-butylphenoL-750 parts by volume of ethanol, cooled to 15", are saturated with hydrogen chloride gas and then diluted by the addition of 4000 parts by volume of ethanol. 2,6-di-t-bzztylphenol (824 parts, is dissolved in the alcoholic solution and a solution of sodium nitrite (304 parts in 400 parts by volume of water) is added at 15-20 over a period of one hour while stirring. Stirring is continued for another 2 hours while allowing the temperature to rise to room temperture. 2000 parts by volume of water are added and the product is then separated by filtration and washed Well with Water. The filter cake is slurried in 3000 parts by volume of petroleum ether, filtered, washed on the filter with 1000 parts by volume of petroleum ether and dried in a vacuum oven at 70-80". The yield of 4-nitroso-2,6-di-t-butylphenol, melting at 219, is 848 parts (90.2%).

"time the temperature rises to 53.

6 (b) 4-amin o- 2,6-di-t-butylphenol.4-nitroso 2,6-di-tbutylphenol (176 parts) is dissolved in 600parts by volume of 5 N sodium hydroxide and 1200 parts by which the product is filtered rapidly, washed with 4000 parts by volume of water and dried in a vacuum desiccator over phosphoric anhydride. The yield of 4-amino-2,6-dit-butylphenol, melting at 105-108 is 162.3 parts (98.5%

3,5-triazine.--A solution of cyanuric chloride (18.4 parts) in boiling acetone parts by volume) is poured in a thin stream while stirring into 200 parts by volume of ice-water, keeping the temperature at 0-5 with external cooling. 4-amino-2,G-di-t-butylphenol (22.1 parts) and sodium carbonate (5.3 parts) are added and the reaction mixture is stirred vigorously at 810 for 45 minutes. The mixture is then diluted by the addition of 100 parts by volume of acetone and stirring is continued for an additional hour at 8-10. The suspension is then poured into 500 parts by volume of icewater, the precipitate is filtered OE and dried in vacuo. The yield of 6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-dichloro-1,3,5-triazine is 34.8 parts (94%). The product melts at 144.

EXAMPLE 2 4,6-bis- (4-hydr0xy-3,5-di-t-butylwnilino -2-chl0r0- 1,3,5-triazine A solution of 4.6 parts of cyanuric chloride in 100 parts by volume of boiling acetone is poured in a thin stream into 200 parts by volume of ice-water While stirring and keeping the temperature at 05 by means of external cooling of the mixture. 4-amino-2,6-di-t-butylphenol (16.7 parts) and sodium bicarbonate (6.3 parts) are then added and the temperature is maintained at 10 for 45 minutes while vigorously stirring; then the temperature is kept at 50 for 45 minutes, and finally at reflux for 45 minutes. The brown solid which precipitates is filtered ofif, washed well with water and petroleum ether and is finally recrystallized from dioxane-hexane (5:4). The product 4,6-bis-(4- hydroxy 3,5 di t butylanilino)-2-chloro-1,3,5-triazine weighs 5.05 parts (37%) and melts under decomposition at 304.

EXAMPLE 3 6-(4-hydroxy-3,5-di-t-butylanilino) -4-n-0ctyllhi02- chl0r0-1,3,5-triazine An alcoholic solution of sodium n-octylmercaptide (prepared by dissolving 0.23 part of sodium in 10 parts by volume of ethanol and adding 1.46 parts of n-octylmercaptan) is added rapidly to a slurry of 3.69 parts of 6-(4- hydroxy 3,5-di-t-butylanilino)-2,4-dichloro-1,3,5-triazine [preparation described in Example 1, (a) through (c)] in 10 parts by volume of ethanol. An immediate exothermic reaction ensues, but external cooling is applied and the reaction mixture is kept at room temperature for /2 hour, after which said mixture is poured into 50 parts by volume of Water and an oil separates which solidifies upon cooling. The 6 (4-hyd-roxy-3,S-di-t-butylanilino)-4-n-octylthio-2- chloro-1,3,5-triazine, thus obtained is filtered, washed with water until free of chloride ion, and finally recrystallized twice from hexane. The purified compound Weighs 2.04 parts (42.5%) and melts at 119-120".

Other substituted triazines which are useful according to the invention are prepared analogously to the methods illustrated in the foregoing examples. The following are some further examples of how such substituted triazines are prepared:

If, in Example 1 (c), 4-amino-2-rnethylphenol is sub stituted for an equimolar amount of 4amino-2,6-di-t-butylphenol, then 6-(4-hydroxy-S-methylanilino)-2,4-dichloro- 6- (4-hydroxy-3,5-di-t-butylanilino)-2,4dichl0r0-1,

1,3,5-triazine is obtained. Alternatively, if in the same example, 4-amino-2-octadecylpheno1 is employed instead,

then 6-(4-hydnoxy-3-octadecylanilino)-2,4-diehloro-1,3,5- triazine is obtained.

If, in Example 3, an equimolar amount of methyl 5 mercaptan is employed in place of octyl mercaptan, then 6 4 (4 -hydroXy-3 ,5 -di-t-butylanilino) -4-met hylthio-2-chlo- 'ro1,3,5-.triazine is obtained.

If, in Example 3, octadecyl mercaptan'is'employed instead of methyl mercaptan as mentioned above, then there is obtained 6-(4-hydroxy-3,5di-t-butylani1ino)-4-octadec- ,y1thio-2-chloro-1,3,5-triazine.

What is claimed is:

1. A compound of the formula:

(lower) alkyl HO- NE 1 (lower) alkyl wherein R is a member selected from the group consisting of dialkylhydroxyanilino and alkylmercapto.

2. 4,6 bis (4-hydroxy-3,S-di-t-butylanilino)-2-chloro- 1,3,5-triazine.

3. 6- (4 hydroxy 3,5-di-t-butylanilino) -4-n-octylthio- 2-chloro-1,3,5-triazine.

References Cited by the Examiner UNITED STATES PATENTS WALTER A. MODANCE, Primary Examiner.

NICHOLAS S. RIZZO, Examiner. 

1. A COMPOUND OF THE FORMULA: 